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Energia Renovable PDF
Energia Renovable PDF
A R T I C L E I N F O A B S T R A C T
Article history: Sustainable economic and industrial growth requires safe, sustainable resources of energy. For the future
Received 3 August 2009 re-arrangement of a sustainable economy to biological raw materials, completely new approaches in
Accepted 9 October 2009 research and development, production, and economy are necessary. The ‘first-generation’ biofuels
appear unsustainable because of the potential stress that their production places on food commodities.
Keywords: For organic chemicals and materials these needs to follow a biorefinery model under environmentally
First generation biofuel sustainable conditions. Where these operate at present, their product range is largely limited to simple
Second generation biofuel
materials (i.e. cellulose, ethanol, and biofuels). Second generation biorefineries need to build on the need
Biorefinery
for sustainable chemical products through modern and proven green chemical technologies such as
Biomass
Bio-oil bioprocessing including pyrolysis, Fisher Tropsch, and other catalytic processes in order to make more
complex molecules and materials on which a future sustainable society will be based. This review focus
on cost effective technologies and the processes to convert biomass into useful liquid biofuels and
bioproducts, with particular focus on some biorefinery concepts based on different feedstocks aiming at
the integral utilization of these feedstocks for the production of value added chemicals.
ß 2009 Elsevier Ltd. All rights reserved.
Contents
1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 579
2. Biomass as multiple feedstocks for biorefinery . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 580
2.1. Biorefinery concept/system . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 581
3. First generation biofuels . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 581
3.1. Conversion processes for first generation biofuels . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 582
3.1.1. Transesterification . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 582
3.2. Whole-crop biorefinery . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 585
3.2.1. Oleochemicals . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 585
3.2.2. De-oil cake . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 587
4. Second generation biofuels . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 587
4.1. Conversion processes for second generation biofuels . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 588
4.1.1. Physical conversion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 588
4.1.2. Thermo-chemical conversion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 588
4.1.3. Hydrotreating of vegetable oils/green diesel . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 590
4.1.4. Bio-oil. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 590
4.1.5. FT oil or green motor fuel from biomass . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 591
4.1.6. Bioethanol from lignocellulosic biomass . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 591
4.1.7. Chemical conversion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 592
5. Types of biorefinery . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 593
5.1. Green biorefinery . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 593
5.2. Forest and lignocellulosic based biorefinery . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 593
* Corresponding author at: Center for Rural Development and Technology, Indian Institute of Technology Delhi, Hauz Khas, New Delhi 110016, India.
Tel.: +91 11 26591162; fax: +91 11 26591121.
E-mail addresses: snn@rdat.iitd.ac.in, naiksn@gmail.com (S.N. Naik).
1364-0321/$ – see front matter ß 2009 Elsevier Ltd. All rights reserved.
doi:10.1016/j.rser.2009.10.003
S.N. Naik et al. / Renewable and Sustainable Energy Reviews 14 (2010) 578–597 579
to review the literature on first and second generation biofuels and Enhancement of biomass utilization requires tremendous effort
anticipated biochemicals from the non-food crop biomass. In this to develop new biomass systems in which production, conversion
respect, the present paper is a part of research program aiming at and utilization of biobased products are carried out efficiently in near
the integrated utilization of Jatropha in India and cereal crop harmony with nature [6]. However, success depends on how far it is
residues in Canada, attempting to contribute to the first generation possible to change today’s production of goods and services
biofuels production (i.e. biodiesel) and parallel use of the residues gradually from fossil to biological raw materials. Therefore many
for energy and 2nd generation biofuels production. In addition researchers around the World are working on the development of
some biorefinery concepts based on different biomass feedstocks possible biomass integrated conversion technologies. For example,
for 2nd generation biofuels and their bioproducts with example Huang et al. [14] reviewed on separation methods and technologies
have been discussed. related to lignocellulosic biorefineries for production of ethanol and
other products. The paper critically has reviewed the current and
2. Biomass as multiple feedstocks for biorefinery future technologies used for corn to ethanol biorefinery, lignocellu-
losic biomass to ethanol biorefinery, integrated lignocellulose/forest
Biomass derived from trees, agro-forest residues, grasses, biorefinery (ILCB), pre extraction of hemicellulose and other value
plants, aquatic plants and crops are versatile and important added chemicals (corn germ, fiber, zein or gluten from corn–ethanol
renewable feed stock for chemical industry as shown in Fig. 2. plant), detoxification of fermentation hydrolyzates, and ethanol
Through photosynthesis process, plants convert carbon dioxide product separation and dehydration. For future biorefineries
and water in to primary and secondary metabolite biochemicals. separation processes like extractive distillation with ionic liquids
Both of these are industrially important chemicals. Primary and hyperbranched polymers, adsorption with molecular sieve and
metabolites are carbohydrate (simple sugar, cellulose, hemicellu- biobased adsorbents, nanofiltration, extractive-fermentation, mem-
lose, starch, etc.) and lignin called lignocellulose present in high brane pervaporation in bioreactors, and vaccum membrane
volume in biomass. The lignocellulosic biomass can be converted distillation (VMD) hold significant potential and great promise for
into biofuels. The secondary metabolite are high value biochem- further investigation, development and application. Clark et al. [16]
icals such as gums, resins, rubber, waxes terpenes, tepenoids, reported the use of green chemical technologies to transform low
steroids, triglyceride, tannin, plant acids, alkaloids, etc. are present value waste biomass to green chemicals like, waxes and ethanol, etc.
in low volume in the plants [15]. The secondary metabolites can be However, Chew et al. [17] have reported on different types of
utilized for production of high value chemicals such as food flavors, catalysts and their role in the catalytic processes for production
feeds, pharmaceuticals, cosmoceuticals, and nutraceutical, etc. of biofuels in a typical palm oil and oil palm based refinery in
using integrated processing technique. Malaysia. Rowlands et al. [18] reported the biorefinery challenges,
S.N. Naik et al. / Renewable and Sustainable Energy Reviews 14 (2010) 578–597 581
opportunities in the context of Australian perspective. Mabee et al. The overview of biorefinery system for producing bioproducts
[5] have assessed the emerging biorefinery sector in Canada. Gomez from biomass was also reported by Kamm et al. [3] and Fernando
et al. [11] reported on the underpinning research necessary to enable et al. [12]. There are many research papers which give the
the cost effective production of liquid fuels from plant biomass, with information on biorefinery concept which uses different feed-
a particular focus on the aspect related to plant cell walls and their stocks such as crops and crop residues, forest residues, green
bioconversion. grasses, lignocellulosic biomass, and industrial waste [3,14,17,19].
For the second generation biofuel non edible oilseeds like According to National Renewable Energy Laboratory, a bior-
jatropha curcas, high erucic mustard, Indian beech (pongamia efinery is a facility that integrates biomass conversion processes
pinnata), green seeds canola and micro algae, etc. can be used for and equipments to produce fuels, chemicals and power from
biofuels including green diesel and whereas, aquatic biomass can biomass. The goal of a biorefinery is to transform biomass into
be utilized for bioethanol and biodiesel. This paper also reviews the useful products using technology and processes. Biomass conver-
current status and future scope of biorefineries in the context of sion required deep understanding of production technology,
first and second generation biofuel by utilizing different biomass. chemistry, conversion technology of biomass, economics and
environmental related issues [20].
2.1. Biorefinery concept/system The development of comparable biorefineries—however not in
the sense of a direct copy of petroleum refinery, it is necessary to
The biorefinery system is based on biomass as processing input produce a broad variety of biobased products in an efficient
(feedstocks) for production of multiple bio-based products. The construction set system. Each biorefinery refines and converts its
basic concept of the biorefinery system is to produce biofuel and corresponding biological raw materials into a multitude of
platform of chemicals from biomass. The detail flow chart on valuable products. The product palette of a biorefinery includes
conversion processes such as physical, chemical, biological, and not only the products produced in the petroleum refinery, but also
thermal or combination of processes with products is shown in in particular products that are not accessible in petroleum
Fig. 3. The earlier papers differentiated three types of biorefineries refineries [21]. Therefore it is necessary to develop new
based on feed stocks, processing flexibilities and products. The first technologies such as (i) lignocellulosic feedstock biorefinery,
one has fixed processing capabilities and uses dry grain as feed including LCF pretreatment and effective separation in lignin,
stocks to produced ethanol, dried distillers grain (DDG)/feed cellulose, and hemicellulose, (ii) further development of thermal,
products and carbon dioxide. The second type biorefineries used chemical, and mechanical processes, (iii) development of biolo-
same feedstock and has more processing flexibilities than first one. gical processes, (iv) combination of substantial conversions, such
It can produce starch, high fructose syrup, ethanol, carbon dioxide, as biotechnological and chemical processes [3]
DDG and corn oil. Third type of biorefinery is most advanced and
can use a mix of biomass feed stocks and produced different 3. First generation biofuels
products by employing combination of technologies. It is based on
both the High Value Low Volume (HVLV) and Low Value High The dramatic rise in oil prices seen in the last decade has also
Volume (LVHV) out put principle. The third type of biorefinery are enabled liquid biofuels to become cost-competitive with petro-
again classified in three categories like, Whole Crop, Green and leum-based transportation fuels, and this has led to a surge in
Lignocellulose feedstock biorefineries, which are in research and research and production around the world. The three main types
development stage [12]. of first generation biofuels used commercially are biodiesel
582 S.N. Naik et al. / Renewable and Sustainable Energy Reviews 14 (2010) 578–597
(bio-esters), ethanol, and biogas of which world wide large them can be utilized for production of various bioproducts. In that
quantities have been produced so far and for which the production respect, example of whole crop biorefinery as shown in Fig. 4, has
process is considered ‘established technology’. Biodiesel is a been discussed aiming at the integrated utilization of Jatropha in
substitute of diesel and is produced through transesterification of India, attempting to contribute to sustainable biodiesel production
vegetable oils, and residual oils and fats, with minor engine and parallel use of its solid residues for production of other
modifications; it can serve as a full substitute as well. Bioethanol is valuable chemicals and utilization of its lignocellulosic biomass for
a substitute of gasoline and it is a full substitute for gasoline in so- 2nd generation biofuels production.
called flexi-fuel vehicles. It is derived from sugar or starch through
fermentation. Bioethanol can also serve as feedstock for ethyl 3.1. Conversion processes for first generation biofuels
tertiary butyl ether (ETBE) which blends more easily with gasoline.
Biogas, or biomethane, is a fuel that can be used in gasoline 3.1.1. Transesterification
vehicles with slight adaptations. It can be produced through The vegetable oil based fatty acid methyl esters (FAME),
anaerobic digestion of liquid manure and other digestible feed- popularly known as biodiesel, is gaining importance as an
stock. At present, biodiesel, bioethanol and biogas are produced environment-friendly diesel fuel substitute or extender. Biodiesel
from commodities that are also used for food. The demands of is an alternative diesel, made from renewable biological sources
edibles oils are increasing trend, so it difficult to use the such as vegetable oils and animal fats by chemically reacting oil or
agricultural food crop for biofuel production [22]. There are some fat with an alcohol, in the presence of a homogeneous and
potential crops for biodiesel production, which can be taken up as heterogeneous catalyst. The product of the reaction is a mixture of
Industrial crop on unproductive lands. Such multipurpose uses methyl esters, which are known as biodiesel, and glycerol, which is
oilseeds crops can be introduced, so that the biomass produced by a high value co-product [23,24].
S.N. Naik et al. / Renewable and Sustainable Energy Reviews 14 (2010) 578–597 583
3.1.1.1. Homogeneous catalysis. Transesterification is a reversible potential to replace homogeneous catalysts, eliminating separa-
reaction and proceeds essentially by mixing the reactants in which tion, corrosion and environmental problems [23].
the catalysts is a liquid acid or a liquid base. The process known as The solid acid catalyzed biodiesel production by simultaneous
transesterification, as shown in Eq. (1) (Transesterification esterification and transesterification of low quality oil containing
(alcoholysis) process). high FFA was performed by Kulkarni et al. [23]. The reaction
(1)
3.1.1.2. Heterogeneous catalysis. It is not possible to perform a mechanism of simultaneous esterification and transesterification
basic transesterification process for high free fatty acid (FFA) using Lewis acid is as shown in Scheme 1. The esterification takes
content oil and decreases the conversion of oil to methyl ester due place between free fatty acids (RCOOH) and methanol (CH3OH)
to saponification reaction. The use of solid catalyst is recom- whereas transesterification takes place between triglyceride
mended for high free fatty acid containing oil. This is because the (RCOOR’) (taken as representative of triglycerides in this case)
solid acid catalysts can simultaneously catalyze the transester- and methanol adsorbed on acidic site (L+) of catalyst surface. The
ification of triglycerides and esterification of free fatty acid (FFA) interaction of the carbonyl oxygen of free fatty acid or mono-
present in oil to methyl esters. Solid acid catalysts have the strong glyceride with acidic site of the catalyst forms carbocation. The
584 S.N. Naik et al. / Renewable and Sustainable Energy Reviews 14 (2010) 578–597
nucleophilic attack of alcohol to the carbocation produces a charides by liquefaction process. The dextrin and oligosaccharides
tetrahedral intermediate (Scheme 1). During esterification the are further hydrolyzed by enzyme such as pullulanase and
tetrahedral intermediate eliminates water molecule to form one glucoamylase in a process known as saccharification. Saccharifica-
mole of ester (RCOOCH3). The transesterification mechanism can tion converts all dextrans to glucose, maltose and isomatose. The
be extended to tri- and di-glyceride. It is well known that mash is then cooled to 30 8C and yeast is added for fermentation
transesterification is a stepwise reaction. In the reaction sequence [26].
the triglyceride is converted stepwise to di- and monoglyceride Ethanol production is usually obtained via enzymatic hydro-
and finally glycerol. The tetrahedral intermediate formed during lysis of starch containing crops like corn wheat. Corn ethanol
reaction eliminates di-, monoglyceride and glycerol when tri-, di- production facilities can be classified into two groups i.e. wet & dry
and monoglyceride come in contact with the acidic sites, mill processes [25]. Dry mills are usually smaller in size (capacity)
respectively, to give one mole of ester (RCOOCH3) in each step. and are built primarily to manufacture ethanol only. According to
In cases, esterification and transesterification produce methyl Shapouri et al. [27] modern wet milling plants are able to produce
ester, the same final product. Also, as shown in Scheme 1, the 1 gal ethanol consuming 35150 Btu of thermal energy and
catalyst is regenerated after the simultaneous esterification and 2134 KWh of electricity. If molecular sieves are used the thermal
transesterification reactions. Use of excess alcohol favors forward energy input drops to 32150 Btu/gal. The starch grain is prepared
reaction and thus maximizes the ester yield [23]. for ethanol fermentation by either wet milling or dry grinding as
shown in Fig. 5a and b. Wet mill ethanol process produced variety
3.1.1.3. Ethanol conversion processes. A wide variety of carbohy- of valuable coproducts such as nutraceuticals, pharmaceuticals,
drates containing raw materials have been used for production of organic acids and solvent. Dry grinding mill process is specially
ethanol by fermentation process. These raw materials are classified designed for production of ethanol and animal feed.
under three major categories:
3.1.1.4. Fermentation process. The term fermentation can generally
(a) Sugar containing crops: Sugar cane, wheat, beet root, fruits, be defined as the metabolic process in which an organic substrate
palm juice, etc.
(b) Starch containing crops: Grain such as wheat, barely, rice,
sweet sorgum, corn, etc. and root plants like potato, cassava.
(c) Cellulosic biomass: Wood and wood waste, cedar, pine, wood,
etc. agricultural residues, fibers.
The alcohol produced from food crops like corn, wheat, barley,
sweet sorgum is called grain alcohol, where as ethanol produced
from lingo-cellulosic biomass such as agro residue (i.e. rice straw,
wheat straw) grasses (switch grass) is known as biomass ethanol or
bioethanol. Both these alcohols are produced through biochemical
process [25].
Chemical structure of starch consists of long chain polymer of
glucose. The macromolecular starch cannot be directly fermented
to ethanol by conventional fermentation technology. The macro-
molecular structure first broke down in to simpler and smaller
glucose. In this process, starch feedstocks are grounded and mixed
with water to produce a mash typically contained 15–20% starch.
The mash is then cooked at or above its boiling point and treated
subsequently with two enzyme preparation. The first enzyme
hydrolyzes starch molecules to short chains to glucose. The first
enzyme is amylase, amylase liberates ‘‘maltodextrin’’ oligosac- Fig. 5. (a) Dry mill process and (b) Wet mill process.
S.N. Naik et al. / Renewable and Sustainable Energy Reviews 14 (2010) 578–597 585
Fig. 7. (a) Basic oleochemicals and downstream oleochemicals and derivatives and (b) basic oleochemicals and downstream oleochemicals and derivatives production
flow.Soon [29].
S.N. Naik et al. / Renewable and Sustainable Energy Reviews 14 (2010) 578–597 587
Table 1
Application of oleochemicals.
Industry/Product Uses
and biofuels (Table 1). In theory, oleochemicals can replace very effective in comparison with conventional surfactants. The
petrochemicals in all their applications [29]. Why oleochemicals? production of protein based surfactant involves hydrolysis of
The reasons are simple First, oleochemicals are derived from protein with sulphuric acid followed by acylation with RCOCl
renewable resources, as compared to petrochemicals which are (R55C12–C18) to form acyl amino acid sodium salts which are
obtained from exhaustible or non-renewable petroleum, Secondly, converted into acylesters of amino acids by esterification with fatty
products derived from oleochemicals are more readily biodegrad- alcohol [30].
able and hence do not pose a threat to the environment, Thirdly,
products derived from petroleum sources use more energy and 4. Second generation biofuels
cause higher emissions of such pollutants as NOx, SO2, CO and
hydrocarbons. Second generation biofuels are produced from biomass in a
more sustainable fashion, which is truly carbon neutral or even
3.2.2. De-oil cake carbon negative in terms of its impact on CO2 concentrations. In
Biomass used for production of biodiesel would generate the context of biofuel production, the term ‘plant biomass’ refers
million tones of residual protein (De-oilcake). The use of protein for largely to lignocellulosic material as this makes up the majority of
non-food applications is currently more limited compared to the the cheap and abundant nonfood materials available from plants
utilization fatty acids derivatives. The edible protein can be utilized [11,31]. At present, the production of such fuels is not cost-
for production of essential amino acids for animal feeds and human effective because there are a number of technical barriers that need
consumption. Some of the nonedible oil seeds cake like jatropha, to be overcome before their potential can be realized. Plant
neem, karanja, etc. would use to produced biopesticides and amino biomass represents one of the most abundant and underutilized
acids for non-food applications. Sanders et al. [30] have reported biological resources on the planet, and is seen as a promising
the application of protein based raw materials for production of source of material for fuels and raw materials. As it is most basic,
1,2-ethanediamine and 1,4-butanediamine from amino acids. The plant biomass can simply be burnt in order to produce heat and
production of amino acids from de-oil cake would add value to electricity. However, there is great potential in the use of plant
biofuel crops produce in large scale. 1,2-Ethanediamine is biomass to produce liquid biofuels. Plant biomass is comprised
produced starting with ethylene by various routes as given in Fig. 8. mostly of plant cell walls, of which typically 75% is composed of
1,2-Ethanediamine and 1,4-butanediamine can be synthesized polysaccharides [32]. These polysaccharides represent a valuable
from amino acids such as serine and arginine respectively. pool of potential sugars, and even in traditional food crops such as
Decarboxylation of serine will form ethanolamine, which is wheat (Triticum aestivum) there is as much sugar tied up in the
converted into diamine by addition of ammonia. Arginine can stems as there is in the starch of the grains. To date, the potential of
be hydrolysed to ornithine and urea. Ornithine will form 1,4- many crop residues, such as straw and wood shavings, to provide
butanediamine after carboxylation. Protein based surfactants are sugar feedstocks for biofuel production has not been realized.
the most valuable mild surfactants. Since the structure and However, biofuel production from agricultural by-products could
properties of the amino acids in the surfactants are similar to the only satisfy a proportion of the increasing demand for liquid fuels.
tissue of the skin amino acids, this cause strong affinity and soft This has generated great interest in making use of dedicated
feeling on skin. Acyl derivatives from glutamic acid and serine are biomass crops as feedstock for biofuel production [22].
Lignocellulosic materials are a collection of feedstocks for
advanced biofuels and can be obtained either through hydrolysis
and fermentation (i.e. bioethanol) or through gasification (i.e.
Fischer–Tropsch bio-diesel, bio-DME and bio-SNG). Typical
resources for these fuels are short rotation forestry crops (poplar,
willow and eucalyptus), perennial grasses (miscanthus, switch
grass and reed canary grass) and residues from the wood industry,
forestry and from agriculture. Advanced biofuels, also referred to
as 2nd generation biofuels, are carbon-based fuels that are
produced by innovative processes mainly using lignocellulosic
materials for which commercial utilization is still under develop-
ment. Bioethanol (advanced) is a substitute of gasoline. It is a full
Fig. 8. Production of 1,2-ethanediamine using various routes. substitute for gasoline in so-called flexi-fuel vehicles. With
588 S.N. Naik et al. / Renewable and Sustainable Energy Reviews 14 (2010) 578–597
hydrolysis, sugars are extracted from lignocellulosic feedstock, content (30–40%). Full pressing requires 95,000 kPa to squeeze out
after which the sugars are fermented into ethanol. Fischer–Tropsch as much oil as possible, preferably up to 3–5% residual fat for
diesel (FT-diesel) or BTL (Biomass-to-Liquids) is a full substitute of animal materials. Full-pressing can also be carried out in a pre-
diesel. Lignocellulosic biomass is gasified to produce syngas which press and a final press [7].
is in turn transformed into liquid hydrocarbons, mostly diesel and
kerosene. Bio-SNG (Synthetic Natural Gas) is a fuel that can be used 4.1.1.2. Briquetting of biomass. Agricultural, forestry residues and
in gasoline vehicles with slight adaptations. Lignocellulosic other waste biomass materials are often difficult to use as biofuels
biomass is gasified to produce syngas which is in turn transformed because of there uneven bulky and troublesome characteristics.
into methane. Bio-DME (Dimethyl Ether) is a fuel that can be used This draw back can be overcome by means of densification of the
in diesel vehicles with slight adaptations. Lignocellulosic biomass residual into compact regular shapes. During densification
is gasified to produce syngas which is in turn transformed into biomass enclosed in compression chambers presses. There are
DME [33]. two major methods of densification, i.e. pressing and maceration.
Some time these two processes are combined, in pressing there is a
4.1. Conversion processes for second generation biofuels close correlation of an increase in density with an increase in
applied pressure in the early stage of compression, but the rate of
There are two main routes available for producing liquid increase in density fall rapidly as the density of pressed material
biofuels from biomass; one involves thermochemical processing approaches the density of water. There is no such close correlation
and the other biochemical processing. Thermochemical processing of density change and degree of maceration, which may be
defines the conversion of biomass into a range of products, by chopping, grinding, and pulverizing. A coarse chopping of some
thermal decay and chemical reformation, and essentially involves materials may be as effective as ultrafine grinding. For example
heating biomass in the presence of different concentrations of tree branches undergo extensive volume reduction when chipped,
oxygen. The clear advantage of thermochemical processing is that but fine grinding would provide little, if any, additional reduction
it can essentially convert all the organic components of the in volume [6,7].
biomass compared with biochemical processing which focuses
mostly on the polysaccharides [11]. This section onwards paper 4.1.1.3. Distillation. Distillation is the most important method for
mainly focuses on the conversion processes for lignocellulosic extracting essential oil and relies on the evaporation of the more
biomass and utilization of combination of technologies for volatile constituents of a blend to separate them from the non-
production of other value added chemicals (Fig. 9) and example volatile parts. Plants are crushed to encourage them to release their
of some biorefineries based on different feedstocks have been oils. The plants are steam distilled, and the essential oils vaporize
discussed aiming at the integrated utilization of biomass. and rise up with the steam. The vapours are captured, and are
allowed to condense back into liquids. A more high tech chemical
4.1.1. Physical conversion process is molecular distillation. It is used to produce fragrances
that cannot be distilled by conventional methods [7].
4.1.1.1. Mechanical extraction. Crude vegetable oils are recovered
from the oil seeds by applying a mechanical pressure using screw 4.1.2. Thermo-chemical conversion
press (expeller). Screw press can be applied in two ways: pre- Biomass can be converted to energy by mainly two processes.
pressing and full pressing. In pre-pressing, only part of the oil is They are either thermo-chemical or biological. The thermo-
recovered and the partially de-oiled meal (cake with 18–20% oil) is chemical conversion process includes direct combustion, gasifica-
further treated by solvent extraction. Combined pre-pressing and tion, liquefaction, and pyrolysis as shown in Fig. 10. When biomass
solvent extraction is commonly applied for oilseeds with high oil is heated under oxygen deficient conditions, it generates synthesis
gas, or syngas, which consists primarily of hydrogen and carbon reducing gases such as CO or H2 and/or catalysts to be present in
monoxide. This syngas can be directly burned or further processed addition to biomass [18].
for other gaseous or liquid products. In this sense, thermal or In the field of thermochemical conversion of biomass,
chemical conversion of biomass is very similar to that of coal [26]. lignocellulosic materials can be converted directly to a liquid
similar to heavy fuel oils by reacting them with synthesis gas in the
4.1.2.1. Direct combustion. Combustion is the chemical reaction presence of suitable catalyst [36]. Aqueous liquefaction of
between a fuel and oxygen which usually takes place in air and is lignocellulosics involves desegregation of the wood ultrastructure,
more commonly known as burning. The products are carbon followed by partial depolymerization of the constitutive com-
dioxide and water with the release of heat. When the direct pounds. In the alkali liquefaction, deoxygenating occurs through
combustion of biomass is conducted in a well vented area, biomass decarboxylation from ester formed by hydroxyl group and formate
burning used for domestic stoves and boilers can be a sound ion derived from carbonate.
substitute for combustion of conventional fissile fuel. Sulfur Alkali salts such as sodium carbonate and potassium carbonate,
emissions (0.05–0.2 wt%) are much lower and the formation of can act as catalyst for hydrolysis of macromolecules such as
particulate can be controlled at the source [26]. cellulose and hemicellulose into smaller fragments. The heavy oil
obtained from the liquefaction process is a viscous tarry lump,
4.1.2.2. Gasification. Generally gasification is not a new technology which sometimes caused troubles in handling. For this reason,
however its use for the conversion of biomass into a viable fuel has some organic solvents (e.g. propanol, butanol, acetone, methyl
only been investigated for past thirty years. Syngas can be produced ethyl ketone, ethyl acetate) need to be added to the reaction
from biomass by two routes namely catalytic and noncatalytic. system. All these solvents, except ethyl acetate, may be reproduced
Noncatalytic process requires a very high temperature of operation, from wood during liquefaction. This suggests that the solvent can
as high as 1300 8C, whereas catalytic process can be operated at be recovered for reuse. The oil yield is reported to be higher with
substantially lower temperature. With more advances in the the catalytic aqueous liquefaction than with the non-catalytic
catalysis, the temperature requirement is expected to go downward aqueous liquefaction. The average oil yield is around 31% in the non
further from the current value of about 900 8C [26]. catalytic process and 63% in the catalytic process [35]. In the
The gasification step involves reacting biomass with air, oxygen, liquefaction process, the amount of solid residue increased in
or steam to produce a gaseous mixture of CO, CO2, H2, CH4, and N2 proportion to the lignin content. Lignin is a macromolecule, which
either known as producer gas or synthesis or syngas, depending on consists of alkylphenols and has a complex three dimensional
the relative proportions of the component gases [18]. Producer gas is structure. It is generally accepted that free phenoxy radicals are
primarily useful as a fuel for stationary power generation, whereas formed by thermal decomposition of lignin above 525 K and that
syngas may be, and is presently, used to make a range of fuels and the radicals have a random tendency to form solid residue through
chemical intermediates. For transportation fuels, the main syngas condensation and polymerization.
derived routes to fuels are hydrogen by water-gas-shift reaction Bio-oil obtained from air dried wood by high pressure
(WGS) [34], hydrocarbons by Fischer–Tropsch (F-T) synthesis or liquefaction (HPL) result in a complex mixture of volatile organic
methanol synthesis followed by further reaction to produce acids, alcohols, aldehydes, ethers, esters, ketones, and non volatile
hydrocarbon or oxygenated liquid fuels [33]. The WGS reaction components. These oils could be upgraded catalytically to yield an
uses CO, H2O to give H2 and CO2. It can be used to upgrade producer organic distillate product which is rich in hydrocarbons and useful
gas to syngas by enriching the H2 content or to produce H2 as an end chemicals. Compared to bio-oil obtained from the fast pyrolysis
product in its own right. F-T synthesis has been used since 1930s to method, their yield from HPL process is much lower and highly
produce hydrocarbon fuels from syngas. The production of methanol viscous [35].
from syngas has been practiced since the 1920s [18].
4.1.2.4. Pyrolysis. The pyrolysis is thermal degradation of biomass
4.1.2.3. Liquefaction. The liquefaction of biomass has been inves- by heat in the absence of oxygen, which results in the production of
tigated in the presence of solution of alkalis, glycerin, propanol, charcoal (solid), bio-oil (liquid), and fuel gaseous products.
butanol or direct liquefaction [35]. Liquefaction usually produces The pyrolysis of biomass has been studied with the final
water insoluble oils of high viscosity and usually requires solvents, objectives of recovering a biofuel with medium-low calorific
590 S.N. Naik et al. / Renewable and Sustainable Energy Reviews 14 (2010) 578–597
char decomposes at a very slow rate and it forms carbon rich solid
residues. diesel, and biodiesel. Green diesel has a higher cetane value and
4.1.2.4.2. Fast pyrolysis. It occurs in the high temperature range of good cold flow properties. It is also has excellent storage stability
850–1250 K with fast heating rate (10–200 K/s), short solid and is completely compatible for blending with the standard mix
residence time (0.5–10 s) and fine particle (<1 mm). The fast of petroleum derived diesel fuels. In contrast to fatty acid methyl
pyrolysis is recommended for production of liquid and/or gaseous esters, green diesel properties do not depend on feed origin and
products. In fast pyrolysis process biomass decomposes to process configuration and the fully deoxygenated biofuel is readily
generate vapours, aerosol, and some charcoal like char. After blended with diesel fuel.
cooling and condensation of vapours and aerosol a dark brown
mobile liquid is formed that has heating value that is half that of 4.1.4. Bio-oil
conventional fuel oil. Fast pyrolysis produced 60–75% of bio-oil, Bio-oil/pyrolysis oil is produced by fast pyrolysis process. In this
15–25% solid char and 10–20% non condensed gases depending process, organic class of compounds, such as cellulose, hemi-
upon feedstocks [37]. cellulose, and lignin, etc. are thermally decomposed at moderate
4.1.2.4.3. Flash pyrolysis. It differs strongly from that of conven- temperature (400–600 8C) in absence of oxygen to produce liquid
tional pyrolysis, which is performed slowly with massive pieces of product viz. bio-oil (60–70%), char (13–25%), and gas such as CO,
wood. It occurs in the temperature range of 1050–1300 K, fast H2, light hydrocarbons (13–25%). The yield and chemical
heating rate (>1000 K/s), short residence time (<0.5 s) and very composition of bio-oil depends upon feed stocks and process
fine particle (<0.2 mm). Bio-oil production from biomass pyrolysis condition: particle size of biomass (2–5 mm), residence time (0.1–
is typically carried out via flash pyrolysis [35] the produced oil can 2 s), and reactor type. In general, reactor types which are presently
be mixed with the char to produce bioslurry. Bioslurry can be more used are; fluidized bed reactor, circulating fluid bed, fast fluidized
easily fed to the gasifier (gasifier condition: 26 bars; 927–1227 K) bed, etc. (Fig. 11). The bio-oil is a dark brown viscous, corrosive and
for efficient conversion to syngas. The conversion of biomass to acidic with distinctive smoky odor used as fuel for boiler, gas
crude oil can have an efficiency of up to 70% for flash pyrolysis turbine, diesel engines, furnaces and stationary engines. Bio-oil has
process. The so called bio-crude can be used in engines and a complex chemical composition contained chemical products of
turbines. Its use as feedstocks for refineries is also being considered lignocelluloses biomass like aliphatic alcohols/aldehydes, fura-
[35,38]. noids, pyranoids, benzenoids, fatty acids and high molecular mass
hydrocarbons, etc. these constituents are mixed with water (25–
4.1.3. Hydrotreating of vegetable oils/green diesel 45%), which is formed in pyrolysis process to form an emulsion
Vegetable oils are renewable feedstock currently being used for with organic constituents. Therefore a wide range of ‘‘Green
production of biofuels from sustainable biomass resources. The
existing technology for producing diesel fuel from plant oils such
as rapeseed, soybean, canola and palm oil are largely centered on
transesterification of oils with methanol to produce fatty acid
methyl esters (FAME) or biodiesel. The future widespread use of
biofuels depends on developing new process technologies to
produce high quality transportation fuels from biologically derived
feedstocks. These new biofuels need to be compatible with the
existing fuel and transportation infrastructure to be economically
feasible.
Researchers around the world are in pursuit of different
processing routes to convert vegetable oils into a high quality
diesel fuel or diesel blend stock that would fully compatible with
petroleum derived diesel fuel. The isoparaffin-rich diesel known as
‘green diesel’ is produced from renewable feedstock containing
triglycerides and fatty acids by process of catalytic saturation,
hydrodeoxygenation, decarboxylation and hydroisomerization.
This technology can be widely used for any type of oil feedstock
to produce an isoparaffin-rich diesel substitute. This product,
referred to as green diesel, is an aromatic and sulfur free diesel fuel
having a very high cetane blending value. The cold flow properties
of the fuel can be adjusted in the process to meet climate-specific
cloud point specifications in either the neat or blended fuel [39].
Table 2 compares the Green diesel fuel properties with petroleum Fig. 11. Fluidized bed fast pyrolysis process.
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Fig. 12. Biomass based FT synthesis process. Fig. 13. Conversion of lignocellulosic biomass to ethanol.
592 S.N. Naik et al. / Renewable and Sustainable Energy Reviews 14 (2010) 578–597
vessel (i.e. digester) and vaporized using saturated steam for a volume of macromolecular compounds (polysaccharide, cellulose,
short time (20 s to 20 min) at a temperature 473–543 K and high hemicellulose, and lignin) called primary metabolite. The other low
pressure 14–16 bar. The pressure in digester is then dropped volume and high value biochemical molecules like terpenoids,
quickly by opening the steam and the material is exposed to waxes, resins, sterols, and alkaloids are known as secondary
normal atmospheric pressure to cause explosion which disinte- metabolites or extractive biomass. In the biorefinery process these
grate lignocellulosic biomass. Different types of devices are chemicals are initially extracted from biomass by using solvent
available for steam explosion. Steam explosion causes the extraction or supercritical fluid extraction. Recently Dewarte et al.
hemicellulose and lignin from the wood to be decomposed and [49], Clark et al. [16] reported integrated straw based biorefinery and
converted into low molecular weight fractions which can be easily isolated high value chemicals like waxes, polycosanol, and sterol by
extracted. Therefore most of the water soluble fraction of using supercritical carbon dioxide. Supercritical fluid extraction can
hemicellulose can be removed by water extraction. At the same be used for extraction of aromatic woods (cedar wood, sadal wood,
time, a part of the low molecular weight fraction of lignin is also pine wood) to isolate extractives. The extracted lignocellulosic
extracted. The xylose can be fermented to ethanol and the lignin biomass is further used for hydrolysis and fermentation for
can be further processed to produce other fuels. The crystalline production of biofuels. The other solvent like, ethanol, acetone,
cellulose remains solid after the pretreatment and later break methanol, water can be used to isolate desired extractive from
down to glucose by enzymatic hydrolysis process. The glucose is biomass [7].
further fermented to alcohol and the hemicellulose fraction is
converted to xylose. The conversion of xylose to ethanol is a 4.1.7.3. Supercritical water conversion of biomass. A supercritical
difficult process, therefore, pretreatment is necessary to reduce the fluid is defined as a substance that is at temperature and pressure
crystallinity of cellulose to lessen the average polymerization of conditions which are above its vapour liquid critical point (for
the cellulose and hemicellulose–lignin sheath that surround the water it is 644 K and 22 MPa; for CO2 it is 304 K and 7.4 MPa). At
cellulose and to increase available surface area for the enzyme to supercritical conditions a fluid is neither liquid nor gas as it can not
attack [25]. be made to boil by decreasing the pressure at constant
Ethanol can be blended with gasoline to produce an oxygenated temperature, and it would not condense by cooling at constant
fuel with lower hydrocarbon and green house gas emissions, pressure [50].
certain aldehydes are increased, which could cause health issues. Supercritical fluid processing of biomass to chemicals repre-
Automobiles can be operated on ethanol/gasoline blends from 5% sents an alternative path to acid hydrolysis, enzymatic hydrolysis
to 25% without any alterations in engine equipments or setting of cellulose to sugars. With acid hydrolysis acid recovery is a costly
[25]. The fuel properties of alcohol blended gasoline and pure and polluting issue. Enzymatic saccarification needs pretreatment
gasoline are given in Table 4. The major engine operation issue of lignocellulosic biomass. Supercritical water can quickly convert
with alcohol blended fuels is fuel quality, volatility, octane number, cellulose to sugar and convert biomass into a mixture of oils,
cold start, hot operation, and fuel consumption. organic acids, alcohol and methane. In supercritical (i.e. 300–
644 K; pressure 200–250 bar) and near critical state (523–573 K)
4.1.7. Chemical conversion acid (H+) and base components (OH) of water are separate and
dissolve in the biomass. The dissolved supercritical water breaks
4.1.7.1. Chemical hydrolysis. The important specific factors in the bonds of cellulose and hemicellulose rapidly to produce small
chemical hydrolysis are surface to volume ratio, acid concentra- sugar molecules, glucose, xylose and oligosaccharide [51,52].
tion, temperature, and time. The surface to volume ratio is These properties make supercritical water a very promising
especially important, in that it also determines the magnitude of reaction medium without using any catalyst for the conversion
the yield of glucose. Hence smaller the particle size the better the of biomass to value added products. The scheme of supercritical
hydrolysis in terms of the extent and rate of reaction. With respect water conversion of biomass and integral utilization side streams
to the liquid to solid ratio, the higher the ratio the faster the of the process is shown in Fig. 14. Supercritical water gasification
reaction [48]. technology has been demonstrated for conversion of cellulose into
glucose in the range of 10–20 s and above 45 s pyrolysis start. As
4.1.7.2. Solvent extraction. Solvent extraction involves different temperature increases to 873 K supercritical water becomes strong
unit operations: extraction of the oil from the oil seeds using oxidant and results in complete disintegration of the substrate
hexane as a solvent; evaporation of the solvent; distillation of the structure by transfer of oxygen from water to the carbon atoms of
oil–hexane mixture (called miscella); and toasting of the de-oiled the substrate. The hydrogen atom of water is set free and form
meal. In special cases, other solvents can be used: halogenated hydrogen. Supercritical water also breaks the cellulosic bonds and
solvents (mostly dichloromethane), acetone, ethanol or isopropa- also formed gaseous products. The typical overall reaction for
nol. Supercritical extraction can also be performed using CO2 [7]. biomass is as follows [53].
Extraction refers to a process in which the desired substance is 2C6 H12 O6 þ 7H2 O ! CO2 þ 2CH4 þ CO þ 15H2
selectively removed from the raw materials by allowing the desired
substance to dissolve into the solvent, and subsequently recovering
the substance from the solvent. To remove the particular substance
from biomass, extraction and separation are both essential. Typically
biomass (wood, wheat straw, aromatic grasses, etc.) contains high
Table 4
Fuel properties of ethanol, gasoline, blended gasoline.
5. Types of biorefinery pigments, crude drugs, and other organics, whereas the green juice
includes proteins, free amino acids, organic acids, dyes, enzymes,
5.1. Green biorefinery hormones, other organic substances, and minerals. The pressed
cake can be also used for the production of green feed pellets, as a
A green biorefinery is a multiproduct system which handles its raw material for the production of chemicals, such as levulinic acid,
refinery cuts, products, and fractions in accordance with the and for conversions to syngas and synthetic fuels.
physiology of the corresponding plant material as described by
Kamm and Kamm [21], Fernando et al. [12] and illustrated in 5.2. Forest and lignocellulosic based biorefinery
Fig. 15. A green biorefinery uses natural wet feedstocks derived
from untreated products, such as grass, green plants, or green crops Lignocellulosic materials contain two types of polysaccharides,
as inputs, which are produced in large quantities in green plants. cellulose and hemicellulose, bound together by a third component,
The first step of the refinery is to treat the green biomass lignin. LCB consists of three basic chemical fractions, (i)
substances in their natural form using wet-fractionation to hemicellulose, sugar molecule of mainly pentoses, (ii) cellulose,
produce a fiber-rich press cake and a nutrient-rich green juice. a glucose polymer, (iii) lignin, polymer of phenols [54]. An
The press cake contains cellulose, starch, valuable dyes and overview of potential products of LCB is shown in Fig. 16. In LCB
syngas stage, biogas stage, carbon rich chains, and plant products.
The concept of LCB based on these stages is described in Fig. 16.
example, palm oil, one of the most productive oil crops yields only polysaccharides, pigments, animal feed, fertilizer and H2). (8) Algae
6000 l of oil per hectare, whereas microalgae oil yield per hectare is can be grown in suitable culture vessel (photo-bioreactor)
around 58,700 l/ha [57]. The potential advantages of algae as throughout the year with an annual biomass production.
feedstocks (biofuels and biomaterials) for biorefinery are as
follows (Fig. 18). 5.4. Integrated biorefinery
(1) Algae synthesize and accumulate large quantities of neutral
lipids/oil (20–50% DCW), (2) High growth rates (1–3 doublings/ The biorefinery types that have been discussed previously are
day), (3) Thrives in saline/brackish water/costal sea water, (4) based on one conversion technology to produce various chemicals.
Algae tolerate marginal lands (e.g. desert, arid and semi arid land) A biorefinery is a capital-intensive project, and when it is based on
that are not suitable for conventional agriculture, (5) Utilize just one conversion technology, as is the case for the previously
growth nutrients such as nitrogen and phosphorus from variety of described biorefineries, it increases the cost of outputs (or
wastewater sources (e.g. Agricultural run off, industrial and products) generated from such biorefineries. Hence, several
municipal waste water), (6) Sequester CO2 from flue gases emitted conversion technologies (thermochemical, biochemical, etc.) can
from fossil fuel fired power plants and other sources there by be combined together to reduce the overall cost, as well as to have
reducing emissions of a major greenhouse gas, (7) Produced value more flexibility in product generation and to provide its own
added co-products or by products (e.g. biopolymers, proteins, power. Fig. 19 provides a schematic of an integrated biorefinery.
Table 5
Physico-chemical properties of bo-oil produced from different biomass.
Properties Wood Cereals (wheat) Rapeseed Crop biomass Sugar cane bagasses
Three different platforms, namely: thermochemical, sugar, and associated technical challenges. However, growing concerns over
nonplatform or existing technologies are integrated. An integrated first generation biofuels in terms of their impact on food prices and
biorefinery produces various products, which include electricity the environment have led to an increasingly bad press in the last
produced from thermochemical and bioproducts from the year. The unfortunate effect is that biofuel is starting to generate
combination of sugar and other existing conversion technology resistance particularly in poor countries with environmental
platforms. agendas. As the replacement of fossil fuels takes place irrespective
An emerging concept in the biorefinery arena is conversion of of these concerns, the way to avoid the negative effects of
bio-oil, the product from biomass pyrolysis, which could be routed producing biofuels from food supplies is to make lignocellulosic-
via a conventional petrochemical refinery to generate various derived fuels available within the shortest possible time (i.e.
chemicals, the typical schematic of the process in shown in Fig. 20. second generation biofuels). However the immediate use of first
The advantage of this route is that all necessary infrastructures for generation biofuels involves putting in place logistic changes to
the separation and purification of products generated are already use biofuels. This commitment to biofuels in the present will make
in place. This concept makes perfect sense since most petroleum the transition to the second generation biofuels more economically
refineries are well equipped to handle variable feedstock with the convenient. But at present the technology to produce these
assumption that no two batches of crude oil are the same. Table 5 replacement fuels is still being developed. Biorefineries based on
gives the composition of bio-oil compounds. Bio-oil chemical lignocellulosics will be able to access a much wider variety of
properties vary with the feedstock but woody biomass typically feedstock, including forest biomass. Therefore, there is a need to
produces a mixture of 30% water, 30% phenolics, 20% aldehydes integrate process operation, reactor and catalyst design to improve
and ketones, 15% alcohols, and 10% miscellaneous compounds the effectiveness of different processes used for bioproducts and
[58]. A process known as hydrodeoxygenation (HDO) could be biofuels production in a typical biorefinery system. The main
applied to replace oxygen by hydrogenation of the raw bio-oils. objective of the biorefinery is to produce multiple products using
After several HDO treatment steps the bio-oil could be transformed combination of technologies. Moreover the commitment of the
into a liquid hydrocarbon with properties similar to those of chemistry, particularly the organic chemistry, needed for the
petroleum crude oil. The deoxygenated bio-oils can potentially be concept of bio-based products and biorefinery systems and to force
refined in existing petroleum refineries, with only minor adjust- the combination of the biotechnological and chemical conversion
ments to the current petroleum industry refinery infrastructure of substances.
that is set up for hydrodesulfurization (HDS) process [59].
Acknowledgements
6. Conclusions
Financial support from Natural Sciences and Engineering
The paper has discussed first and second generation biofuel, Research Council of Canada (NSERC), and Canada Research Chair
concept of biorefineries, different types of biorefineries, and (CRC) funding to Dr. A.K. Dalai, is gratefully acknowledged.
S.N. Naik et al. / Renewable and Sustainable Energy Reviews 14 (2010) 578–597 597